Poly chlorinated polyethylene

Heat stabilizers protect polymers from the chemical degrading effects of heat or uv irradiation. These additives include a wide variety of chemical substances, ranging from purely organic chemicals to metallic soaps to complex organometaUic compounds. By far the most common polymer requiring the use of heat stabilizers is poly(vinyl chloride) (PVC). However, copolymers of PVC, chlorinated poly(vinyl chloride) (CPVC), poly(vinyhdene chloride) (PVDC), and chlorinated polyethylene (CPE), also benefit from this technology. Without the use of heat stabilizers, PVC could not be the widely used polymer that it is, with worldwide production of nearly 16 million metric tons in 1991 alone (see Vinyl polymers). 

Siding. The resin most used for siding is poly(vinyl chloride) homopolymer, compounded with modifiers, stabilizers, and pigments. Modifiers are most often acryhc esters, followed by chlorinated polyethylene or ethylene—vinyl acetate, used at 6—8 phr (parts per hundred resin). The modifier increases the impact strength of the rigid PVC. 

At one time butadiene-acrylonitrile copolymers (nitrile rubbers) were the most important impact modifiers. Today they have been largely replaced by acrylonitrile-butadiene-styrene (ABS) graft terpolymers, methacrylate-buta-diene-styrene (MBS) terpolymers, chlorinated polyethylene, EVA-PVC graft polymers and some poly acrylates. 

Chlorinated Polyethylene Polyethylene-Ethylacrylote Polyethylene-Vinyl acetate Polyethylene-Methacryllc Acid Polyphenyleneoxlde Poly-4 mef ylpentene(1) Polyethylene... 

Elurocaibon elastomers Acrylic elastomers Polyurethanes Polyethylene Chlorinated polyethylene Poly(vinyl chloride)... 

Chlorinated poly (vinyl chloride) (CPVC) has increased Tg compared to PVC, and this increases its upper use temperature. Applications include hot- and cold-water pipe as well as pipe for the handling of industrial chemical liquids. Chlorinated polyethylene (CPE) finds use as roofing and other vapor barrier membranes, as pond liners, and as an additive to improve the impact strength of PVC. 

ABA ABS ABS-PC ABS-PVC ACM ACS AES AMMA AN APET APP ASA BR BS CA CAB CAP CN CP CPE CPET CPP CPVC CR CTA DAM DAP DMT ECTFE EEA EMA EMAA EMAC EMPP EnBA EP EPM ESI EVA(C) EVOH FEP HDI HDPE HIPS HMDI IPI LDPE LLDPE MBS Acrylonitrile-butadiene-acrylate Acrylonitrile-butadiene-styrene copolymer Acrylonitrile-butadiene-styrene-polycarbonate alloy Acrylonitrile-butadiene-styrene-poly(vinyl chloride) alloy Acrylic acid ester rubber Acrylonitrile-chlorinated pe-styrene Acrylonitrile-ethylene-propylene-styrene Acrylonitrile-methyl methacrylate Acrylonitrile Amorphous polyethylene terephthalate Atactic polypropylene Acrylic-styrene-acrylonitrile Butadiene rubber Butadiene styrene rubber Cellulose acetate Cellulose acetate-butyrate Cellulose acetate-propionate Cellulose nitrate Cellulose propionate Chlorinated polyethylene Crystalline polyethylene terephthalate Cast polypropylene Chlorinated polyvinyl chloride Chloroprene rubber Cellulose triacetate Diallyl maleate Diallyl phthalate Terephthalic acid, dimethyl ester Ethylene-chlorotrifluoroethylene copolymer Ethylene-ethyl acrylate Ethylene-methyl acrylate Ethylene methacrylic acid Ethylene-methyl acrylate copolymer Elastomer modified polypropylene Ethylene normal butyl acrylate Epoxy resin, also ethylene-propylene Ethylene-propylene rubber Ethylene-styrene copolymers Polyethylene-vinyl acetate Polyethylene-vinyl alcohol copolymers Fluorinated ethylene-propylene copolymers Hexamethylene diisocyanate High-density polyethylene High-impact polystyrene Diisocyanato dicyclohexylmethane Isophorone diisocyanate Low-density polyethylene Linear low-density polyethylene Methacrylate-butadiene-styrene... 

MC MDI MEKP MF MMA MPEG MPF NBR NDI NR OPET OPP OSA PA PAEK PAI PAN PB PBAN PBI PBN PBS PBT PC PCD PCT PCTFE PE PEC PEG PEI PEK PEN PES PET PF PFA PI PIBI PMDI PMMA PMP PO PP PPA PPC PPO PPS PPSU Methyl cellulose Methylene diphenylene diisocyanate Methyl ethyl ketone peroxide Melamine formaldehyde Methyl methacrylate Polyethylene glycol monomethyl ether Melamine-phenol-formaldehyde Nitrile butyl rubber Naphthalene diisocyanate Natural rubber Oriented polyethylene terephthalate Oriented polypropylene Olefin-modified styrene-acrylonitrile Polyamide Poly(aryl ether-ketone) Poly(amide-imide) Polyacrylonitrile Polybutylene Poly(butadiene-acrylonitrile) Polybenzimidazole Polybutylene naphthalate Poly(butadiene-styrene) Poly(butylene terephthalate) Polycarbonate Polycarbodiimide Poly(cyclohexylene-dimethylene terephthalate) Polychlorotrifluoroethylene Polyethylene Chlorinated polyethylene Poly(ethylene glycol) Poly(ether-imide) Poly(ether-ketone) Polyethylene naphthalate Polyether sulfone Polyethylene terephthalate Phenol-formaldehyde copolymer Perfluoroalkoxy resin Polyimide Poly(isobutylene), Butyl rubber Polymeric methylene diphenylene diisocyanate Poly(methyl methacrylate) Poly(methylpentene) Polyolefins Polypropylene Polyphthalamide Chlorinated polypropylene Poly(phenylene oxide) Poly(phenylene sulfide) Poly(phenylene sulfone)... 

Blending of polymers is an attractive method of producing new materials with better properties. Blends of aliphatic polyesters, especially of poly(e-CL), have been investigated extensively and have been the subject of a recent review paper [170]. Poly(e-CL) has been reported to be miscible with several polymers such as PVC, chlorinated polyethylene, SAN, bisphenol A polycarbonate, random copolymers of Vdc and VC, Vdc and AN, and Vdc/VAc, etc. A single composition-dependent Tg was obtained in the blends of each of these polymers with poly(e-CL). This is of interest as a polymeric plasticizer in these polymers. Blends of PVC and poly(e-CL) with less than 50 wt % of poly(e-CL) were homogeneous and exhibited a single Tg. These blends were soft and pliable because the inherent crystallinity of poly(e-CL) was destroyed and PVC was plasticized... 

Flow-induced miscibility was also found for blends of poly(ethylene-co-vinyl acetate) and solution chlorinated polyethylene undergoing simple shear flow at... 

On the other hand, some mechanically compatible blends as well as some dispersed two-phase systems have made respectable inroads into the commercial scene. Many of these are blends of low-impact resins with high-impact elastomeric polymers examples are polystyrene/rubber, poly (styrene-co-acrylonitrile) /rubber, poly (methyl methacrylate) /rubber, poly (ethylene propylene)/propylene rubber, and bis-A polycarbonate/ ABS as well as blends of polyvinyl chloride with ABS or PMMA or chlorinated polyethylene. 

PB PBI PBMA PBO PBT(H) PBTP PC PCHMA PCTFE PDAP PDMS PE PEHD PELD PEMD PEC PEEK PEG PEI PEK PEN PEO PES PET PF PI PIB PMA PMMA PMI PMP POB POM PP PPE PPP PPPE PPQ PPS PPSU PS PSU PTFE PTMT PU PUR Poly(n.butylene) Poly(benzimidazole) Poly(n.butyl methacrylate) Poly(benzoxazole) Poly(benzthiazole) Poly(butylene glycol terephthalate) Polycarbonate Poly(cyclohexyl methacrylate) Poly(chloro-trifluoro ethylene) Poly(diallyl phthalate) Poly(dimethyl siloxane) Polyethylene High density polyethylene Low density polyethylene Medium density polyethylene Chlorinated polyethylene Poly-ether-ether ketone poly(ethylene glycol) Poly-ether-imide Poly-ether ketone Poly(ethylene-2,6-naphthalene dicarboxylate) Poly(ethylene oxide) Poly-ether sulfone Poly(ethylene terephthalate) Phenol formaldehyde resin Polyimide Polyisobutylene Poly(methyl acrylate) Poly(methyl methacrylate) Poly(methacryl imide) Poly(methylpentene) Poly(hydroxy-benzoate) Polyoxymethylene = polyacetal = polyformaldehyde Polypropylene Poly (2,6-dimethyl-l,4-phenylene ether) = Poly(phenylene oxide) Polyp araphenylene Poly(2,6-diphenyl-l,4-phenylene ether) Poly(phenyl quinoxaline) Polyphenylene sulfide, polysulfide Polyphenylene sulfone Polystyrene Polysulfone Poly(tetrafluoroethylene) Poly(tetramethylene terephthalate) Polyurethane Polyurethane rubber... 

Doube, C. P. Walsh, D. J., "Studies of Poly(vinyl chloride)/Solution Chlorinated Polyethylene Blends by Inverse Gas Chromatography," Eur. 

In situ polymerisation does not however guarantee homogeneous blends as two phase regions can exist within the polymer/polymer/monomer three component phase diagram. In the case of vinyl chloride polymerisation with solution chlorinated polyethylene, the vinyl chloride has limited solubility in both poly(vinyl chloride) and chlorinated polyethylene. The phase diagram has the form shown in Fig. 3 The limit of swelling of vinyl chloride in the chlorinated polyethylene is A and the highest concentration of PVC prepared by a one-shot polymerisation is B. 

Fig. 9. Dynamic mechanical analysis plots of tan 5 against temperature for chlorinated polyethylene (52 % Cl) (4) and blends with poly(butyl acrylate) containing (3) 84.7% PBA, (2) 64.1 % PBA, and (1) 46.1 % PBA. The inset shows a plot of T, against weight percent chlorinated polyethylene where there is a marked deviation from linearity indicative of a specific interaction...

Strength of the specific interaction. An example of this is shown in Fig. 9 for blends of poly(butyl acrylate) with chlorinated polyethylene. In this case the blend requires a higher activation energy than its additivity value in the form of heat to allow chain movements. A review of this subject and of the relations between and chemical structure of blends has been given by Cowie For miscible blends many attempts have been made to correlate the with the blend composition as is frequently done with random copolymers. Several miscible blends studied by Hammer and Hichman and Ikeda exhibit a composition dependence of which can be described by the simple Fox relationship. 

Fig. 15. DiiTerential thermal analysis traces of a blend of chlorinated polyethylene with poly(methyl methacrylate) obtained by heating at a rate of 10 °C/min. The blend was kept at the quoted temperatures for 10 min. and was quenched prior to scanning. The appearance of two T s after treatment at 190 C is indicative of phase separation at this temperature...

One example in this category is the case of one polymer in two stereoregular forms Other examples are of two polymers which are chemically very similar such as poly(methyl acrylate) with poly(vinyl acetate) A series of systems which have been studied in some detail are various mixtures of chlorine containing polymers. Blends of chlorinated PVC with PVC have been studied It has been suggested that at 65.2 % wt.- % chlorine they are miscible and at 67.5 wt.- % they are not. Chlorinated polyethylene with 45 wt.- % chlorine has also been found to be miscible with PVC In this case it was suggested that phase separation occurs on heating. 

Simulation studies have also been carried out on blends of chlorinated polyethylene with poly(butyl acrylate). The results are shown in Fig. 30. It was found in this case (in a similar way to the previous example) that with the value of X obtained from heat of mixing studies at 70 °C on oligomers (—94 atm) and with the value of Qjj necessary to match the spinodal to the minimum of the cloud point (—0.235 atm/K.) the resulting spinodal was very flat bottomed and lay outside the cloud point curve, an impossible situation. To match the spinodal to the cloud point curve a much smaller value of Xj2 (and correspondingly Qij) must be chosen. This discrepancy could have resulted from differences between the low molecular weight materials used for heat... 

Fig. 30. The experimental cloud point curve (dotted line) and simulated spinodals for blends of poly(butyl acrylate) with a chlorinated polyethylene. The initial value of X,2 = —94 atm obtained from heat of mixing data, and Che adjusted Q,2 = —0.235 atm K" give a curve which is too flat-bottomed (1). By adjusting X j using an appropriate Qjj) a closer fit can be obtained X2) Xj2 = -30Qi2 = -0.076 (3) Xjj = -10 Qjj = -0.026 (4) Xi2 = -1 Qij =. 0034 ...

As reported by Diehl et al. [58], interpolymers are also compatible with a broader range of polymers, including styrene block copolymers [59], poly(vinyl chloride) (PVC)-based polymers [60], poly(phenylene ethers) [61] and olefinic polymers such as ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer and chlorinated polyethylene. Owing to their unique molecular structure, specific ESI have been demonstrated as effective blend compatibilizers for polystyrene-polyethylene blends [62,63]. The development of the miscibility/ compatibility behavior of ESI-ESI blends differing in styrene content will be highlighted below. 

The polymer microstructure based on triad intensities in pyrolysates has been evaluated for poly(styrene-co-butyl acrylate), poly(styrene-co-methyl methacrylate), poly(vinyl chloride-co-vinylidene chloride), poly(styrene-co-maleic anhydride), and for chlorinated polyethylene considered as a copolymer of polyethylene and vinyl chloride [30]. 

Pyrolysis products of chlorinated polyethylene contain molecules similar to those found in polyethylene pyrolysates and, in addition, compounds similar to that obtained from vinyl chloride (significant amount of HCI). Chlorosulfonated polyethylene typically contains only about 1.5% sulfur, but sulfur-containing compounds such as SO2 can be detected among its pyrolysis products. The distribution of chlorine atoms in chlorinated polyethylene has been investigated using Py-GC [55, 56]. The polymer was considered equivalent with a terpoiymer poly[ethylene-co-(vinyl chloride)-co-(1,2-dichloroethylene)]. The level of specific degradation products such as aromatic molecules (benzene + toluene + styrene + naphthalene), chlorobenzene, and dichlorobenzenes correlates well with the carbon/chlorine ratio in the polymer. 

Figure 2. Experimental data on copolymer resist sensitivities in relation to constituent monomer mole fraction. The following references and abbreviations are used P(ST-CMS), chloromethylated polystyrene (8) P(ST-CS), chlorinated polystyrene ( ) P(ST-IS), iodi-nated polystyrene (100 P(ET-CE), chlorinated polyethylene ( 6)a P(ET-BE), brominated polyethylene C165a P(ST-GMA), poly (styrene glycidyl methacrylate)...

Figure 9. Spectra of poly(vinyl chloride), carboxylated poly(vinyl chloride), chlorinated polyethylene (36% chlorine), and ethylene/acrylic acid copolymer (20% acrylic acid).

---